Particulate Organic Research Articles

Large Porewater‐Derived Carbon Outwelling Across Mangrove Seascapes Revealed by Radium Isotopes

AbstractMangrove‐dominated coastlines have high carbon sequestration capacity, but it remains unclear whether tidally outwelled carbon is transformed within the coastal ocean or exported offshore. Here, we used radium isotopes (224Ra and 223Ra) to investigate carbon outwelling in two mangrove seascapes in Brazil across multiple spatial scales. We sampled porewaters to define the source composition, mangrove creek waters to resolve tidal cycles, and cross‐shelf transects to trace outwelling in coastal seascapes. Radium isotopes were positively correlated with dissolved inorganic (DIC), organic (DOC) and particulate organic (POC) carbon across the seascapes. DIC was the primary form of carbon (mean ± SD), representing 85% of the total carbon pool as bicarbonate (75 ± 11%), carbonate (6 ± 5%), and CO2 (4 ± 9%). DOC and POC accounted for 10 ± 6% and 5 ± 6% of total carbon, respectively. Although mangrove waters emitted CO2 to the atmosphere (38–143 mmol m−2 d−1), both bays and continental shelves were a CO2 sink (−2.5 to −0.5 mmol m−2 d−1) associated to chlorophyll‐a enrichments (r2 = 0.86). Total carbon outwelled from mangroves were 3–4 times higher than soil carbon burial at both mangrove sites. Bicarbonate export (27–72 mmol m−2 d−1) to the continental shelf was the major fate of carbon outwelling, more than doubling the perceived capacity of mangrove soil to sequester carbon. Hence, disregarding outwelling as a blue carbon sink mechanism would lead to underestimated assessments of how mangroves capture CO2 and help to mitigate climate change.

Conservation agriculture's impact on total and labile organic carbon pools in calcareous and non-calcareous floodplain soils under a sub-tropical rice-based system.

To evaluate the effects of conservation agriculture (CA) on SOC pools and their lability, field experiments (2015-2020) were conducted on contrasting soils under subtropical climates. The experiment on non-calcareous soils, was comprised of tillage (minimum [MT] vs. conventional [CT]) in main plots, cropping systems (Wheat [Triticum aestivum]-Aus and Aman rice [Oryza sativa L.], WRR; Lentil [Lens culinaris]-Aus and Aman rice, LRR; and Mustard [Brassica nigra]- Boro and Aman rice, MRR) in the sub-plots, and crop residue (with or without 20% residue) in the sub-sub plots. The experiment on calcareous soils, was comprised of tillage (strip-till, ST; no-till, NT; and CT) and crop residue (high residue, HR at 50% by height vs. low residue, LR at 15%). Results showed that the MT had higher SOC contents by 18.8% than the CT in non-calcareous soils. Likewise, SOC was 12.5% and 6.7% higher in the NT and ST, respectively, than in the CT in calcareous soils. Significantly higher particulate organic (POC), permanganate oxidizable (POXC), and microbial biomass carbon (MBC) were observed in the MT, NT, and ST than in the CT at both locations. Reduced tillage with residue retention under LRR had a higher SOC, including labile C pools compared to WRR and MRR systems. Similarly, carbon management index (1.2-1.5 and 1.0-1.2) in both soils had significant positive correlations with SOC lability via POXC, POC, and MBC pools, indicating a SOC sequestration potential. In conclusion, our results showed positive effects of CA on SOC and its lability across soils.

Particulate organic emissions from incense-burning smoke: Chemical compositions and emission characteristics

Incense burning is a common practice in Asian cultures, releasing hazardous particulate organics. Inhaling incense smoke can result in adverse health effects, yet the molecular compositions of incense-burning organics have not been well investigated due to the lack of measurement of intermediate-volatility and semi-volatile organic compounds (I/SVOCs). To elucidate the detailed emission profile of incense-burning particles, we conducted a non-target measurement of organics emitted from incense combustion. Quartz filters were utilized to trap particles, and organics were analyzed by a comprehensive two-dimensional gas chromatography-mass spectrometer (GC × GC–MS) coupled with a thermal desorption system (TDS). To deal with the complex data obtained by GC × GC–MS, homologs are identified mainly by the combination of selected ion chromatograms (SICs) and retention indexes. SICs of 58, 60, 74, 91, and 97 were utilized to identify 2-ketones, acids, fatty acid methyl esters, fatty acid phenylmethyl esters, and alcohols, respectively. Phenolic compounds contribute the most to emission factors (EFs) among all chemical classes, taking up 24.5 % ± 6.5 % of the total EF (96.1 ± 43.1 μg g−1). These compounds are largely derived from the thermal degradation of lignin. Biomarkers like sugars (mainly levoglucosan), hopanes, and sterols are extensively detected in incense combustion fumes. Incense materials play a more important role in shaping emission profiles than incense forms. Our study provides a detailed emission profile of particulate organics emitted from incense burning across the full-volatility range, which can be used in the health risk assessments. The data processing procedure in this work could also benefit those with less experience in non-target analysis, especially GC × GC–MS data processing.

Dynamic of riverine pCO2, biogeochemical characteristics, and carbon sources inferred from δ13C in a subtropical river system

Rivers significantly contribute to the global carbon budget, but data limitations and uncertainty are hampered by CO2 quantification in the global rivers. Thus, this study estimated riverine pCO2 by employing the pH-alkalinity-temperature method, and dissolved inorganic (DIC), dissolved organic (DOC), particulate organic (POC) carbon, and their isotopes (δ13C) with Chlorophyll-a (Chl a) were measured in river water samples from 26 sampling sites for characterization and source identification in the Yangtze River system. The estimated pCO2 varies from (120 ppm) to (3400 ppm) with an average (1085 ppm) across the Yangtze River and pCO2 is almost three times oversaturated than the ambient air (380 ppm). The downstream sites pronounced elevated pCO2 than the upstream sites. The relationship of δ13CDIC and pCO2 indicated that pCO2 control is seasonally independent. The significant correlations between DOC, POC, and pCO2 revealed that organic carbon influenced pCO2 in the river. The seasonal fluctuations of pCO2 were observed with an average of (762.23 ppm) and (1407.35 ppm) in winter and summer, respectively. δ13CDIC showed that the metabolic process has a negligible influence on DIC, δ13CDIC, and pCO2. δ13CDIC values increased from −8.95‰ to −4.91‰ during summer, whereas winter increased from −19.76‰ to −1.97‰ suggesting that DIC derived from carbonate weathering, dissolution of atmospheric and soil CO2. The δ13CDOC (−30.43‰ to −24.05‰) and δ13CPOC (−29.87‰ to −23.37‰) values confirmed that organic carbon mainly derived from the degradation of organic materials in soil. δ13CDIC revealed that anthropogenic sewage discharge slightly modified DIC composition. Overall, this study provides new insight into recent seasonal fluctuations of the pCO2, DOC, POC, DIC, δ13C, and their inputs. Thus, these variations and inputs of carbon transported by the Yangtze River could have a significant influence not only on the biogeochemical cycle and ecosystem process but also on the global carbon budget.

Barium stable isotopes as a fingerprint of biological cycling in the Amazon River basin

Abstract. The biological cycle of rock-derived nutrients on the continents is a major component of element transfer between the Earth's surface compartments, but its magnitude currently remains elusive. The use of the stable isotope composition of rock-derived nutrients, which can be fractionated during biological uptake, provides a promising path forward with respect to quantifying biological cycling and its overall contribution to global element cycling. In this paper, we rely on the nutrient-like behaviour of the trace element barium (Ba) and use its elemental and stable isotope compositions in dissolved and sediment load river samples to investigate biological cycling in the Amazon Basin. From these measurements, we show that dissolved Ba mainly derives from silicate rocks, and a correlation between dissolved Ba and K abundances suggests that biological cycling plays a role in the Ba river budget. Furthermore, the isotope composition of Ba (δ138Ba) in the dissolved load was found to be significantly different from that of the parent silicate rocks, implying that dissolved Ba isotopic signatures are affected by (i) the precipitation of soil-forming secondary phases as well as (ii) biological uptake and release from dead organic matter. Results from an isotope mass balance method applied to the river dissolved load data indicate that, after its release to solution by rock weathering, Ba is partitioned between the river dissolved load, secondary weathering products (such as those found in soils and river sediments), and the biota. In most sub-catchments of the Amazon, river Ba abundances and isotope compositions are significantly affected by biological cycling. Relationships between estimates of Ba cycled through biota and independent metrics of ecosystem dynamics (such as gross primary production and terrestrial ecosystem respiration) allow us to discuss the role of environmental parameters such as climate or erosion rates on the biological cycling of Ba and, by extension, the role of major rock-derived nutrients. In addition, catchment-scale mass and isotope budgets of Ba show that the measured riverine export of Ba is lower than the estimated delivery of Ba to the Earth surface through rock alteration. This indicates the existence of a missing Ba component, which we attribute to the formation of Ba-bearing particulate organics (possibly accumulating as soil organic matter or currently growing biomass within the catchments) and to organic-bound Ba exported as “unsampled” river particulate organic matter. Given our findings on the trace element Ba, we explore whether the river fluxes of most major rock-derived nutrients (K, Mg, Ca) might also be significantly affected by biological uptake or release. A first-order correction of river-derived silicate weathering fluxes from biological cycling shows that the carbon dioxide (CO2) consumption by silicate weathering at the mouth of the Amazon could be several times higher than the previously reported value of 13 × 109 mol CO2 yr−1 (Gaillardet et al., 1997). Overall, our study clearly shows that the chemical and isotope compositions of rivers in the Amazon – and most likely in other large river basins – bear a biological imprint, thereby challenging common assumptions made in weathering studies.

A 15-million-year-long record of phenotypic evolution in the heavily calcified coccolithophore <i>Helicosphaera</i> and its biogeochemical implications

Abstract. The biogeochemical impact of coccolithophores is defined not only by their overall abundance in the oceans but also by wide ranges in physiological traits such as cell size, degree of calcification and carbon production rates between different species. Species' sensitivity to environmental forcing has been suggested to relate to their cellular PIC : POC (particulate inorganic carbon : particulate organic carbon) ratio and other physiological constraints. Understanding both the short-term and longer-term adaptive strategies of different coccolithophore lineages, and how these in turn shape the biogeochemical role of the group, is therefore crucial for modeling the ongoing changes in the global carbon cycle. Here we present data on the phenotypic evolution of a large and heavily calcified genus Helicosphaera (order Zygodiscales) over the past 15 million years (Myr), at two deep-sea drill sites in the tropical Indian Ocean and temperate South Atlantic. The modern species Helicosphaera carteri, which displays ecophysiological adaptations in modern strains, was used to benchmark the use of its coccolith morphology as a physiological proxy in the fossil record. Our results show that, on the single-genotype level, coccolith morphology has no correlation with growth rates, cell size or PIC and POC production rates in H. carteri. However, significant correlations of coccolith morphometric parameters with cell size and physiological rates do emerge once multiple genotypes or closely related lineages are pooled together. Using this insight, we interpret the phenotypic evolution in Helicosphaera as a global, resource-limitation-driven selection for smaller cells, which appears to be a common adaptive trait among different coccolithophore lineages, from the warm and high-CO2 world of the middle Miocene to the cooler and low-CO2 conditions of the Pleistocene. However, despite a significant decrease in mean coccolith size and cell size, Helicosphaera kept a relatively stable PIC : POC ratio (as inferred from the coccolith aspect ratio) and thus highly conservative biogeochemical output on the cellular level. We argue that this supports its status as an obligate calcifier, like other large and heavily calcified genera such as Calcidiscus and Coccolithus, and that other adaptive strategies, beyond size adaptation, must support the persistent, albeit less abundant, occurrence of these taxa. This is in stark contrast with the ancestral lineage of Emiliania and Gephyrocapsa, which not only decreased in mean size but also displayed much higher phenotypic plasticity in their degree of calcification while becoming globally more dominant in plankton communities.

The roles of vegetation, tide and sediment in the variability of carbon in the salt marsh dominated tidal creeks

Combined effects of vegetation, tide and sediment on the carbon dynamics in the intertidal creek-marsh systems remain unclear. We investigated the variability of dissolved organic (DOC) and inorganic carbon (DIC), and particulate organic (POC) and inorganic carbon (PIC) in the tidal creeks within the Poaceae and Cyperaceae communities on flood-ebb cycle in a salt marsh of eastern China. In the Poaceae creek with high plant biomass and soil carbon stock, the DOC concentrations were higher by on average 1.00–1.48 times than that in the Cyperaceae creek across all seasons and spring and neap tide stages, while the difference of DIC was not notable. The POC and PIC concentrations were lower in the Poaceae creek compared to the Cyperaceae creek. Spring tides increased the carbon concentrations (except for PIC) in both creeks by on average 7–40%, relative to neap tides. Seasonal variations of sedimentary rate within the communities probably result in the discrepancy of particulate carbon loading between the creeks. The Poaceae creek functioned as a source of DOC and DIC throughout a year but as a sink of POC and PIC in summer and autumn, while it turned to a weak source of PIC in winter and spring. The Cyperaceae creek exhibited as a source of all carbon components throughout a year. We suggest that vegetation type (with soil carbon stocks), tidal regimes and sedimentary dynamics would synergistically determine the fate of carbon in the creeks. Our results are helpful in reliable estimates of carbon transport between the coastal marsh and the adjacent ocean.

Combined effects of CO2 level, light intensity, and nutrient availability on the coccolithophore Emiliania huxleyi

Continuous accumulation of fossil CO2 in the atmosphere and increasingly dissolved CO2 in seawater leads to ocean acidification (OA), which is known to affect phytoplankton physiology directly and/or indirectly. Since increasing attention has been paid to the effects of OA under the influences of multiple drivers, in this study, we investigated effects of elevated CO2 concentration under different levels of light and nutrients on growth rate, particulate organic (POC) and inorganic (PIC) carbon quotas of the coccolithophorid Emiliania huxleyi. We found that OA treatment (pH 7.84, CO2 = 920 μatm) reduced the maximum growth rate at all levels of the nutrients tested, and exacerbated photo-inhibition of growth rate under reduced availability of phosphate (from 10.5 to 0.4 μmol l−1). Low nutrient levels, especially lower nitrate concentration (8.8 μmol l−1 compared with 101 μmol l−1), decreased maximum growth rates. Nevertheless, the reduced levels of nutrients increased the maximum PIC production rate. Decreased availability of nutrients influenced growth, POC and PIC quotas more than changes in CO2 concentrations. Our results suggest that reduced nutrient availability due to reduced upward advective supply because of ocean warming may partially counteract the negative effects of OA on calcification of the coccolithophorid.

Geomorphological controls on fluvial carbon storage in headwater peatlands

AbstractGeomorphological controls and catchment sediment characteristics control the formation of floodplains and affect their capacity to sequester carbon. Organic carbon stored in floodplains is typically a product of pedogenic development between periods of mineral sediment deposition. However, in organically‐dominated upland catchments with a high sediment load, eroded particulate organics may also be fluvially deposited with potential for storage and/or oxidation. Understanding the redistribution of terrestrial carbon laterally, beyond the bounds of river channels is important, especially in eroding peatland systems where fluvial particulate organic carbon exports are often assumed to be oxidised. Floodplains have the potential to be both carbon cycling hotspots and areas of sequestration. Understanding of the interaction of carbon cycling and the sediment cascade through floodplain systems is limited.This paper examines the formation of highly organic floodplains downstream of heavily eroded peatlands in the Peak District, UK. Reconstruction of the history of the floodplains suggests that they have formed in response to periods of erosion of organic soils upstream. We present a novel approach to calculating a carbon stock within a floodplain, using XRF and radiograph data recorded during Itrax core scanning of sediment cores. This carbon stock is extrapolated to the catchment scale, to assess the importance of these floodplains in the storage and cycling of organic carbon in this area. The carbon stock estimate for the floodplains across the contributing catchments is between 3482‐13460 tonnes, equating on an annualised basis to 0.8‐4.5% of the modern‐day POC flux. Radiocarbon analyses of bulk organic matter in floodplain sediments revealed that a substantial proportion of organic carbon was associated with re‐deposited peat and has been used as a tool for organic matter source determination. The average age of these samples (3010 years BP) is substantially older than Infrared Stimulated Luminesence dating which demonstrated that the floodplains formed between 430 and 1060 years ago. Our data suggest that floodplains are an integral part of eroding peatland systems, acting as both significant stores of aged and eroded organic carbon and as hotspots of carbon turnover. © 2019 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.

Speciated and total emission factors of particulate organics from burning western US wildland fuels and their dependence on combustion efficiency

Abstract. Western US wildlands experience frequent and large-scale wildfires which are predicted to increase in the future. As a result, wildfire smoke emissions are expected to play an increasing role in atmospheric chemistry while negatively impacting regional air quality and human health. Understanding the impacts of smoke on the environment is informed by identifying and quantifying the chemical compounds that are emitted during wildfires and by providing empirical relationships that describe how the amount and composition of the emissions change based upon different fire conditions and fuels. This study examined particulate organic compounds emitted from burning common western US wildland fuels at the US Forest Service Fire Science Laboratory. Thousands of intermediate and semi-volatile organic compounds (I/SVOCs) were separated and quantified into fire-integrated emission factors (EFs) using a thermal desorption, two-dimensional gas chromatograph with online derivatization coupled to an electron ionization/vacuum ultraviolet high-resolution time-of-flight mass spectrometer (TD-GC × GC-EI/VUV-HRToFMS). Mass spectra, EFs as a function of modified combustion efficiency (MCE), fuel source, and other defining characteristics for the separated compounds are provided in the accompanying mass spectral library. Results show that EFs for total organic carbon (OC), chemical families of I/SVOCs, and most individual I/SVOCs span 2–5 orders of magnitude, with higher EFs at smoldering conditions (low MCE) than flaming. Logarithmic fits applied to the observations showed that log (EFs) for particulate organic compounds were inversely proportional to MCE. These measurements and relationships provide useful estimates of EFs for OC, elemental carbon (EC), organic chemical families, and individual I/SVOCs as a function of fire conditions.

Population-specific responses in physiological rates of <i>Emiliania huxleyi</i> to a broad CO<sub>2</sub> range

Abstract. Although coccolithophore physiological responses to CO2-induced changes in seawater carbonate chemistry have been widely studied in the past, there is limited knowledge on the variability of physiological responses between populations from different areas. In the present study, we investigated the specific responses of growth, particulate organic (POC) and inorganic carbon (PIC) production rates of three populations of the coccolithophore Emiliania huxleyi from three regions in the North Atlantic Ocean (Azores: six strains, Canary Islands: five strains, and Norwegian coast near Bergen: six strains) to a CO2 partial pressure (pCO2) range from 120 to 2630 µatm. Physiological rates of each population and individual strain increased with rising pCO2 levels, reached a maximum and declined thereafter. Optimal pCO2 for growth, POC production rates, and tolerance to low pH (i.e., high proton concentration) was significantly higher in an E. huxleyi population isolated from the Norwegian coast than in those isolated near the Azores and Canary Islands. This may be due to the large environmental variability including large pCO2 and pH fluctuations in coastal waters off Bergen compared to the rather stable oceanic conditions at the other two sites. Maximum growth and POC production rates of the Azores and Bergen populations were similar and significantly higher than that of the Canary Islands population. This pattern could be driven by temperature–CO2 interactions where the chosen incubation temperature (16 ∘C) was slightly below what strains isolated near the Canary Islands normally experience. Our results indicate adaptation of E. huxleyi to their local environmental conditions and the existence of distinct E. huxleyi populations. Within each population, different growth, POC, and PIC production rates at different pCO2 levels indicated strain-specific phenotypic plasticity. Accounting for this variability is important to understand how or whether E. huxleyi might adapt to rising CO2 levels.

Physiological responses of coccolithophores to abrupt exposure of naturally low pH deep seawater.

Upwelling is the process by which deep, cold, relatively high-CO2, nutrient-rich seawater rises to the sunlit surface of the ocean. This seasonal process has fueled geoengineering initiatives to fertilize the surface ocean with deep seawater to enhance productivity and thus promote the drawdown of CO2. Coccolithophores, which inhabit many upwelling regions naturally ‘fertilized’ by deep seawater, have been investigated in the laboratory in the context of ocean acidification to determine the extent to which nutrients and CO2 impact their physiology, but few data exist in the field except from mesocosms. Here, we used the Porcupine Abyssal Plain (north Atlantic Ocean) Observatory to retrieve seawater from depths with elevated CO2 and nutrients, mimicking geoengineering approaches. We tested the effects of abrupt natural deep seawater fertilization on the physiology and biogeochemistry of two strains of Emiliania huxleyi of known physiology. None of the strains tested underwent cell divisions when incubated in waters obtained from <1,000 m (pH = 7.99–8.08; CO2 = 373–485 p.p.m; 1.5–12 μM nitrate). However, growth was promoted in both strains when cells were incubated in seawater from ~1,000 m (pH = 7.9; CO2 ~560 p.p.m.; 14–17 μM nitrate) and ~4,800 m (pH = 7.9; CO2 ~600 p.p.m.; 21 μM nitrate). Emiliania huxleyi strain CCMP 88E showed no differences in growth rate or in cellular content or production rates of particulate organic (POC) and inorganic (PIC) carbon and cellular particulate organic nitrogen (PON) between treatments using water from 1,000 m and 4,800 m. However, despite the N:P ratio of seawater being comparable in water from ~1,000 and ~4,800 m, the PON production rates were three times lower in one incubation using water from ~1,000 m compared to values observed in water from ~4,800 m. Thus, the POC:PON ratios were threefold higher in cells that were incubated in ~1,000 m seawater. The heavily calcified strain NZEH exhibited lower growth rates and PIC production rates when incubated in water from ~4,800 m compared to ~1,000 m, while cellular PIC, POC and PON were higher in water from 4,800 m. Calcite Sr/Ca ratios increased with depth despite constant seawater Sr/Ca, indicating that upwelling changes coccolith geochemistry. Our study provides the first experimental and field trial of a geoengineering approach to test how deep seawater impacts coccolithophore physiological and biogeochemical properties. Given that coccolithophore growth was only stimulated using waters obtained from >1,000 m, artificial upwelling using shallower waters may not be a suitable approach for promoting carbon sequestration for some locations and assemblages, and should therefore be investigated on a site-by-site basis.

Particulate organics degradation and sludge minimization in aerobic, complete SRT bioreactors

The study evaluates the assumption that in activated sludge processes and under specific operating conditions, the considered unbiodegradable particulate organic fractions of influent (XU) organic solids and biomass decay residues (cell debris, XE) are degraded. The evaluation was performed by comparing sludge observed yield (Yobs) evolution in two full scale, complete solids retention time (SRT), aerobic bioreactors, to the predictions of two activated sludge models. The results showed that in steady state operating conditions of complete solids retention AS processes very low solids accumulation occur. In these conditions, solids accumulation is slightly affected by kinetic coefficients and significantly affected by XU and XE degradation rates. High endogenous residues degradation rate values of 0.05 d−1 and 0.02 d−1 were estimated for the two bioreactors, resulting in low solids accumulation, calculated at 1.6 tons and 3.59 tons per year respectively, of which 1.37 and 0.87 tons were non volatile suspended solids. Depending on WWTP operating conditions the endogenous residues degradation rate is the limiting factor of solids accumulation and consequently for particulate organics degradation.

Biodegradability of wastewater and activated sludge organics in anaerobic digestion

The investigation provides experimental evidence that the unbiodegradable particulate organics fractions of primary sludge and waste activated sludge calculated from activated sludge models remain essentially unbiodegradable in anaerobic digestion. This was tested by feeding the waste activated sludge (WAS) from three different laboratory activated sludge (AS) systems to three separate anaerobic digesters (AD). Two of the AS systems were Modified Ludzack – Ettinger (MLE) nitrification-denitrification (ND) systems and the third was a membrane University of Cape Town (UCT) ND and enhanced biological P removal system. One of the MLE systems and the UCT system were fed the same real settled wastewater. The other MLE system was fed raw wastewater which was made by adding a measured constant flux (gCOD/d) of macerated primary sludge (PS) to the real settled wastewater. This PS was also fed to a fourth AD and a blend of PS and WAS from settled wastewater MLE system was fed to a fifth AD. The five ADs were each operated at five different sludge ages (10–60d). From the measured performance results of the AS systems, the unbiodegradable particulate organic (UPO) COD fractions of the raw and settled wastewaters, the PS and the WAS from the three AS systems were calculated with AS models. These AS model based UPO fractions of the PS and WAS were compared with the UPO fractions calculated from the performance results of the ADs fed these sludges. For the PS, the UPO fraction calculated from the AS and AD models matched closely, i.e. 0.30 and 0.31. Provided the UPO of heterotrophic (OHO, fE_OHO) and phosphorus accumulating (PAO, fE_PAO) biomass were accepted to be those associated with the death regeneration model of organism “decay”, the UPO of the WAS calculated from the AS and AD models also matched well - if the steady state AS model fE_OHO = 0.20 and fE_PAO = 0.25 values were used, then the UPO fraction of the WAS calculated from the AS models deviated significantly from those calculated with the AD models. Therefore in plant wide wastewater treatment models the characterization of PS and WAS as defined by the AS models can be applied without modification in AD models. The observed rate limiting hydrolysis/acidogenesis rates of the sludges are listed.

Dynamic carbon budget of a large shallow lake assessed by a mass balance approach

To study the role of large and shallow hemiboreal lakes in carbon processing, we calculated a 3-year carbon mass balance for Lake Vortsjarv (Estonia) based on in situ measurements. This balance took into account hydrological and biogeochemical processes affecting dissolved inorganic (DIC), dissolved organic (DOC) and particulate organic (POC) carbon species. Accumulation varied greatly on a seasonal and yearly basis. The lake exported carbon during most of the year except during spring floods and in late autumn. In-lake processes were responsible for exporting POC and storing DOC while DIC switched between storage and export. The carbon cycle was alternatively dominated in 2009 by biogeochemical processes and in 2011 by riverine fluxes, whereas in 2010 the two process types were of the same magnitude. These results suggest that the role of large shallow lakes like Vortsjarv in the global C cycle is equally driven by hydrological factors, in particular seasonal water level changes, and by biogeochemical in-lake reactions.

Benthic remineralization in the northwest European continental margin (northern Bay of Biscay)

We report a dataset of sediment characteristics and biogeochemical fluxes at the water–sediment interface at the northwest European continental margin (northern Bay of Biscay). Cores were obtained in June 2006, May 2007 and 2008, at 18 stations on the shelf break (120–180 m), and at 2 stations on the continental slope (520 and 680 m). Water–sediment fluxes of dissolved oxygen (O 2), total alkalinity (TA), nitrate ( NO 3 − ), and dissolved silicate (DSi) were measured at a total of 20 stations. Sediment characteristics include: grain size, chlorophyll- a (Chl- a) and phaeopigment (Phaeo) content, particulate organic (POC) and inorganic (PIC) carbon content, and lead-210 ( 210Pb) and thorium-234 ( 234Th) activities. Sediments were sandy (fine to coarse) with organic matter (OM) (1.0–4.0%) and Chl- a (0.01–0.95 μg g −1) contents comparable to previous investigations in the same region, and a relatively high PIC fraction (0.8–10.2%). Water–sediment O 2 fluxes (−2.4 to −8.4 mmol O 2 m −2 d −1) were low compared to other coastal environments and correlated well with OM and Chl- a content. 234Th activity profiles indicated that Chl- a sediment content was mainly controlled by physical mixing processes related to local hydrodynamics. The correlation between water–sediment fluxes of O 2 and NO 3 − indicated a close coupling of nitrification/denitrification and total benthic organic carbon degradation. Dissolution of biogenic silica (0.05–0.95 mmol m −2 d −1) seemed uncoupled from organic carbon degradation, as characterized by water–sediment O 2 fluxes. The link between water–sediment fluxes of TA and O 2 indicated the occurrence of metabolic driven dissolution of calcium carbonates (CaCO 3) in the sediments (∼0.33±0.47 mmol m −2 d −1), which represented ∼1% of the pelagic calcification rates due to coccolithophores measured during the cruises. These CaCO 3 dissolution rates were below those reported in sediments of continental slopes and of the deep ocean, probably due to the high over-saturation with respect to CaCO 3 of the water column overlying the continental shelf sediments of the northern Bay of Biscay. Rates of total benthic organic carbon degradation were low compared to water column rates of primary production and aphotic community respiration obtained during the cruises.

Nighttime chemical evolution of aerosol and trace gases in a power plant plume: Implications for secondary organic nitrate and organosulfate aerosol formation, NO3 radical chemistry, and N2O5 heterogeneous hydrolysis

Nighttime chemical evolution of aerosol and trace gases in a coal‐fired power plant plume was monitored with the Department of Energy Grumman Gulfstream‐1 aircraft during the 2002 New England Air Quality Study field campaign. Quasi‐Lagrangian sampling in the plume at increasing downwind distances and processing times was guided by a constant‐volume balloon that was released near the power plant at sunset. While no evidence of fly ash particles was found, concentrations of particulate organics, sulfate, and nitrate were higher in the plume than in the background air. The enhanced sulfate concentrations were attributed to direct emissions of gaseous H2SO4, some of which had formed new particles as evidenced by enhanced concentrations of nucleation‐mode particles in the plume. The aerosol species were internally mixed and the particles were acidic, suggesting that particulate nitrate was in the form of organic nitrate. The enhanced particulate organic and nitrate masses in the plume were inferred as secondary organic aerosol, which was possibly formed from NO3 radical‐initiated oxidation of isoprene and other trace organic gases in the presence of acidic sulfate particles. Microspectroscopic analysis of particle samples suggested that some sulfate was in the form of organosulfates. Microspectroscopy also revealed the presence of sp2 hybridized C = C bonds, which decreased with increasing processing time in the plume, possibly because of heterogeneous chemistry on particulate organics. Constrained plume modeling analysis of the aircraft and tetroon observations showed that heterogeneous hydrolysis of N2O5 was negligibly slow. These results have significant implications for several issues related to the impacts of power plant emissions on air quality and climate.

Effect of the heterotrophic dinoflagellate Oxyrrhis marina and the copepod Acartia tonsa on vertical carbon flux in and around thin layers of the phytoflagellate Isochrysis galbana

Dynamics of material and energy flow through food webs differ when resources are allocated in patches in comparison to situations in which the same resources are distributed evenly throughout the water column. Thin layers of plankton are special cases of such resource patches. While previous studies have predominantly focused on the response of organisms to these layers, we investigated how 2 types of grazers in turn affect thin layers. In an experimental study with tightly controlled environmental conditions, we monitored the redistribution of particulate organic (POC), dissolved organic (DOC) and inorganic (DIC) carbon from thin layers of Isochrysis galbana. The 2 grazers (the protist Oxyrrhis marina and the copepod Acartia tonsa) had significant grazing impact on the thin layers despite the fact that their population maxima were observed outside the layers. Both grazers exported carbon from the thin layer as body burden (i.e. incorporated into cell tissue) and through release of DOC and DIC into the environment above and below the layers, albeit at different rates. The copepods released larger amounts of DIC and DOC within the thin layer, while the protist grazer exported more dissolved carbon (DOC and DIC) from the thin layers. In the copepod treat- ments, a net increase of DIC was observed inside the thin layer (as a result of increased respiration during feeding) and into the atmosphere above the water column due to their vertical migration between the thin layer and the water surface. Whether or not grazers made a positive contribution to DOC net release depended on the strength of grazing, with a negative effect when phytoplankton— itself releasing DOC—was depleted.

Mixing and phase partitioning of primary and secondary organic aerosols

[1] Predicting primary and secondary organic aerosol (POA and SOA) concentrations requires understanding the phase partitioning of semi-volatile organic species. A well-mixed single phase organic aerosol can absorb greater amounts of semi-volatile species but little experimental evidence exists on the phase distribution of particulate organics. We investigated the phase partitioning and mixing of semi-volatile POA and SOA in a smog chamber. Particle time of flight (PToF) data from an Aerodyne aerosol mass spectrometer (AMS) were used to quantify the extent of mixing. The SOA plus motor oil and diesel fuel combination produced a weakly mixed system, in which two particulate organic phases coexist. However, the POA in diesel exhaust readily mixed with SOA, forming a single phase after one hour. Although both POA types contain semi-volatile components, there is a fundamental difference in their partitioning behavior with SOA. The high resolution AMS data reveal minor differences in composition between the two types of POA. This work provides further evidence that there exists a set of unidentified components that influence particulate mixing that affect OA formation and suggests the extent of absorbent phase mixing (strong versus weak) can be observed and quantified with PToF data.

A summer time series of particulate carbon in the air and snow at Summit, Greenland

Carbonaceous particulate matter is ubiquitous in the lower atmosphere, produced by natural and anthropogenic sources and transported to distant regions, including the pristine and climate‐sensitive Greenland Ice Sheet. During the summer of 2006, ambient particulate carbonaceous compounds were characterized on the Greenland Ice Sheet, including the measurement of particulate organic (OC) and elemental (EC) carbon, particulate water‐soluble organic carbon (WSOC), particulate absorption coefficient (σap), and particle size‐resolved number concentration (PM0.1–1.0). Additionally, parallel ∼50‐day time series of water‐soluble organic carbon (WSOC), water‐insoluble organic carbon (WIOC), and elemental carbon (EC) were quantified at time increments of 4–24 h in the surface snow. Measurement of atmospheric particulate carbon found WSOC (average of 52 ng m−3) to constitute a major fraction of particulate OC (average of 56 ng m−3), suggesting that atmospheric organic compounds reaching the Greenland Ice Sheet in summer are highly oxidized. Atmospheric EC (average of 7 ng m−3) was well‐correlated with σap (r = 0.95) and the calculated mass‐absorption cross‐section (average of 24 m2 g−1) appears to be similar to that measured using identical techniques in an urban environment in the United States. Comparing surface snow to atmospheric particulate matter concentrations, it appears the snow has a much higher OC (WSOC+WIOC) to EC ratio (205:1) than air (10:1), suggesting that snow is additionally influenced by water‐soluble gas‐phase compounds. Finally, the higher‐frequency (every 4–6 h) sampling of snow‐phase WSOC revealed significant loss (40–54%) of related organic compounds in surface snow within 8 h of wet deposition.